Non-emissive, flame-retardant coating compositions

ABSTRACT

The invention relates to room temperature-curable, non-emissive, flame-retardant coating compositions. The main resin for the coating compositions is a flame-retardant polymer selected from an air dryable flame-retardant polymer, a room-temperature curable mixture of a flame-retardant polymer and curing agent therefor, and mixtures thereof. The solvent for the coating composition is selected from water, a liquid, curable, non-flame promoting solvent and mixtures thereof. The novel liquid, curable, non-flame promoting solvent comprises a liquid polyhalogenated organic ring compound substituted with an air-dryable group.

The present invention was developed during the course of work onDepartment of the Navy Contracts Nos. N00167-78-C-0083 andN00167-79-C-0222.

This application is a division of application Ser. No. 199,843, filedOct. 23, 1980, now U.S. Pat. No. 4,405,761.

BACKGROUND OF THE INVENTION

The present invention relates to flame-retardant coating compositionsand more particularly to such coatings which are non-emissive.

For present purposes, a non-emissive coating composition is a coatingcomposition, an applied film of which does not evolve or emit anyorganic components thereof, lincluding solvent, except for water duringcuring thereof. Non-emissive coatings are required, for example, forcoating the interior of submarines when such submarines are at sea,because adequate ventilation to protect personnel aboard the submarinefrom volatile organic components cannot be effectively and adequatelyprovided. Thus, the need for coating compositions which at most evolvewater during the drying or curing of the coating composition afterapplication. Further, such coatings should be flame-retardant in orderto protect the substrate upon which the coating is applied as well as toretard the spread of fire. While non-emissive, flame-retardant coatingcompositions would appear on the surface to be easy to formulate, itmust be remembered that such coatings cannot be formulated at theexpense of desirable coatings characteristics such as, for example,flow, leveling, application viscosity, can stability, room temperaturecure, and like desirable coatings characteristics. More on this can befound in the Dick et al report "Development of a Nonemissive GeneralPurpose Paint for Submarine Interior Application," Final Report forPeriod Sept. 1, 1978-Aug. 31, 1979; David W. Taylor Naval Ship Researchand Development Center, 31 Aug. 1979, the disclosure of which isincorporated expressly herein by reference.

The coating compositions of the present invention meet such diverseperformance requirements as outlined above and as will be more fullyappreciated based on the disclosure contained herein.

BROAD STATEMENT OF THE INVENTION

The present invention relates to room temperature-curable, non-emissive,flame-retardant coating compositions. The main resin for the coatingcomposition is a flame-retardant polymer selected from an air-dryableflame-retardant polymer, a room-temperature curable mixture of aflame-retardant polymer and curing agent therefor, and mixtures thereof.The solvent for the coating composition is selected from water, aliquid, curable, non-flame promoting solvent and mixtures thereof. Thenovel liquid, curable, non-flame promoting solvent comprises a liquidpolyhalogenated organic ring compound substituted with an air-dryablegroup.

Since coating compositions may require surface-active agents orsurfactants in order to emulsify some resins in water, the novel coatingcomposition of the present invention optionally will contain anon-emissive, non-flame promoting, surface-active agent. Suchsurface-active agent is selected from a non-emissive, non-flamepromoting non-ionic surface-active compound containing a surface-activenonionic group and a halogenated group; a curable, non-flame promoting,cationic surface-active compound containing a halogenated group and acurable group; and a curable, non-flame promoting, anionicsurface-active compound containing a halogenated group and a curablegroup. The novel coating composition of the present invention containsat least one of the non-emissive, non-flame promoting surface-activeagents or the curable, non-flame promoting solvent delineated above.

Another aspect of the present invention is an improved method for makinga coating composition essentially non-emissive, wherein the coatingcomposition comprises an polyepoxide resin and a resinous polyamine orpolyamide hardener therefor. The hardener contains lower molecularweight emissive amine components. Such improvement comprises mixing atrapping agent with the hardener to react preferentially with saidemissive amine components thereof for forming a non-emissive adduct.Such non-emissive adduct optionally may be protonated with aproton-donating acid to make an intrinsic, non-emissive, cationicsurface-active agent. The trapping agent is an epoxy or analpha-,beta-ethylenically unsaturated carbonyl compound.

A further aspect of the present invention is a method for retarding(super) halogenated flame-retardant resins (e.g. epoxide resins) fromcrystallizing from solution and for improving their dispersibility inwater. This method comprises reacting at least a fraction of thehalogenated resin with a long chain aliphatic group (e.g. a higher fattyacid). Unexpectedly, the resulting reaction product renders the blend ofresin and reaction product retardant to crystallizing from solution andstably dispersible in water.

Advantages of the present invention include coating compositions whichare totally non-emissive of organic components. Any organic solvent,cosolvent, or surfactants in the coating composition are non-flamepromoting and are curable. This means that the advantages of retaininggood coatings' properties while adhering to non-emissive andflame-retardant specifications can be met. Another advantage is that thecoatings desirably are aqueous for ease of application and cleanup orare true 100% solids coatings. These and other advantages will bereadily apparent to those skilled in the art based upon the disclosureherein contained.

DETAILED DESCRIPTION OF THE INVENTION

The present invention grew out of the development of non-emissivecoatings primarily intended for the interior of submarines wherevolatilization of organic components from the coatings cannot betolerated while the submarine is at sea due to the limited closedenvironment therein. It should be recognized, however, that theflame-retardant, non-emissive coatings of the present invention have afar wider applicability in that the coatings are not onlyflame-retardant but also are non-emissive for reduction of organicvolatiles from the room temperature curing film which provides greaterenvironmental safety to those people applying the paint and to thosepeople in the vicinity of the drying paint films. The roomtemperature-curable, non-emissive, flame-retardant coating compositionof the present invention is unique in that conventional coatings'properties are retained while other desirable attributes ofnon-emissivity and flame-retardancy are provided. Moreover, the coatingcomposition of the present invention has the flexibility, depending uponits intended formulation and ultimate end use, to contain cosolventsand/or surfactants which are non-emissive and non-flame promoting. Suchsolvents and surfactants increase the effective non-volatile solidscontent of the coating composition as well as replace conventionalsolvents and surfactants which often are volatile or emissive duringroom temperature curing of the applied film of the coating compositionof the present invention and often are flammable. Moreover, the coatingcomposition of the present invention additionally has the flexibility ofbeing able to be formulated as an essentially 100% non-volatile solidscoating composition wherein the liquid, curable, non-flame promotingsolvent is used in such coating composition.

Referring now to the novel solvents of the present invention, suchsolvents are liquid by definition. This means that the solvents areliquid under application conditions and storage conditions of thecoating composition which typically comprehends temperatures oftenranging from as low as about 10° C. on up to about even 50° C. onoccasion, though normally such temperatures for application and curingof the coating composition range from about 20° C. to about 30° C. (roomtemperature). The novel solvents of the present invention are curableand non-flame promoting. By non-flame promoting is meant that thesolvents will not promote the spread of fire nor will they support afire. Such recalcitrance to the propogation of fire may be termedfire-retardancy under some definitions, though no such requirementshould be placed as a limitation on the solvents of the presentinvention. That the solvents do not promote fire is sufficient forpresent purposes, though it is admitted that some novel solvents may beflame-retardant also. Non-flame promotability of the solvents isachieved through polyhalogenation, and desirably, such polyhalogenationis provided by a halogenated ring group. Suitable halogenated groupsinclude aromatic rings, carbocyclic rings including polycyclic and fusedrings, and even heterocyclic rings on occasion. Preferably, thenon-flame promotability of the solvents is derived from apolyhalogenated aromatic group or a polyhalogenated norbornene group.

Another feature unique to the novel solvents of the present invention istheir non-emissiveness which is due to their curability. Curability ofthe novel solvents is achieved by providing functionality or a groupwhich will air-dry to achieve such curing. Suitable groups which provideair-dry curing capability of the solvents of the present inventioninclude, for example, an oxirane-functional group (for linking with anamine, for example), an allyl ether group, or an air-dryable groupderived from a fatty acid. Of course, other functionalities can berelied upon for achieving air-dry capability of the solvents of thepresent invention as will be appreciated by those skilled in the art.

Accordingly, the liquid, curable, non-flame promoting solvents of thepresent invention can be represented by the following structure:##STR1## where: h is halogen,

B is an air-dryable group,

n is at least 2, and

m is at least 1.

Advantageously, h is chlorine or bromine, B is an air-dryable group asnoted above, n is 4 or 5, and m is 1 or 2. Note that the polyhalogenatedaromatic ring may be substituted by another group which may or may notcontain air-dryable functionality.

Preferred solvents of the present invention include those solventsrepresented by the following general structures: ##STR2## In theforegoing structures, R is an organic group which may containair-dryable functionality as noted above. Typically, R is selected froman alkyl group, an allyl group, a haloalkyl group, an acrylic group, analicyclic group, and an aromatic group. B¹ is an air-dryable group.

Representative polyhalogenated cyclic compounds which can be used informulating the solvents of the present invention include, for exampletetrachlorophthalic anhydride (TCPA), pentachlorophenol (PCP),pentabromophenol (PBP),1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride (HCNDA)and the like. Typical reaction schemes for synthesis of the novelsolvents of the present invention utilizing the preferredpolyhalogenated cyclic groups can be as follows. TCPA may be reactedwith any alcohol to cause the anhydride ring to open for forming aTCPA-half-ester. The alcohol used in this reaction can be an alkylalcohol, an allyl alcohol, a haloalkyl alcohol, an acrylic alcohol, orany other alcohol as is necessary, desirable, or convenient. Examples ofsuch alcohols include, for example, methanol, ethanol, and higherstraight chain or branched aliphatic mono-alcohols;2,2,2-trichloroethanol; 2,3-propenol; hydroxyethyl acrylate,hydroxyethyl methacrylate, and related monool esters of acrylic andmethacrylic acids; fatty acid hydroxy esters such as the reactionproduct of an unsaturated fatty acid with an epoxy; and the like.

The TCPA-half ester then can be reacted with a glycidyl allyl ether toform the desired solvent of the present invention. It should be notedthat HCNDA may be used in place of TCPA in the foregoing synthesisscheme.

For forming solvents from PCP or PBP, the PCP and PBP are derivatizedfor further reaction as follows. The PCP or PBP can be reacted withepichlorohydrin or other halohydrin in the presence of a base forforming a glycidyl ether of PCP of PBP. This glycidyl ether then can befurther reacted with an air-dryable fatty acid to provide air dryingcapability to the solvents. Representative air-dryable fatty acidsinclude linoleic acid, linolenic acid, and the like. It will beappreciated that the foregoing synthesis schemes are merely illustrativeand that other reaction schemes may be contemplated for forming thesolvents of the present invention as those skilled in the art willappreciate. The examples will further amplify the preferred reactionschemes for forming the novel solvents of the present invention.

Referring now to the non-emissive, non-flame promoting, non-ionicsurface-active compounds containing a halogenated cyclic group, suchnon-ionic surfactants optionally may be contained in the coatingcomposition of the present invention for improving physicalcharacteristics of the coating composition for application and/or toassist in stabilizing the flame-retardant polymer of the coatingcomposition. While such non-ionic surfactants may be made curable in thecoating composition, they need only be made non-emissive in order tocomply with the precepts of the present invention. Non-flamepromotability of the non-ionic surfactants is the same as defined abovefor the novel solvents. Their synthesis typically comprehends thereaction of a polyhalogenated cyclic compound (such as those describedabove) with a conventional non-ionic surface-active compound. Of course,the ultimate molecular weight of the surface-active compound should besuch that it is non-volative or non-emissive under room temperaturecuring conditions of the coating composition. Typical conventionalnon-ionic surface-active compounds which may be used in forming thenon-emissive, non-flame promoting, non-ionic surface-active agent of thepresent invention include, for example, polyoxyalkylene compoundsincluding polyoxyalkylene alcohols and polyoxyalkylene glycols. Ofcourse, other conventional non-ionic surface-active agents may be usedas is necessary, desirable, or convenient in conventional fashion.

Typical synthesis schemes for forming the non-emissive, non-flamepromoting non-ionic surfactant of the present invention include reactinga polyhalogenated phenol with an alkylene oxide in the presence of aboron trifluoride-etherate or similar catalyst. Alternatively, TCPA canbe reacted with a monoalcohol containing an air-drying or reactivehydroxyl group followed by the reaction of this half-ester of TCPA withan alkylene oxide for forming the non-ionic surfactant. Otherconventional reaction schemes can be envisioned for forming thenon-ionic surfactants of the present invention as will be readilyapparent to those skilled in the art.

Referring now to the novel non-emissive, non-flame-promoting cationicsurfactants of the present invention, such cationic surfactants containa cationic group, a source of flame-retardancy such as a polyhalogenatedgroup, and a group which is air-drying or reactive under roomtemperature curing conditions for linking such cationic surfactant intothe cured film of the coating composition. Preferred polyhalogenation isprovided from polyhalogenated rings such as those described above.Amines and thiols are preferred for providing the cationic functionalityto the surfactants, though other onium groups (e.g. phosphonium groups)broadly may have utility in the invention. The novel cationicsurfactants of the present invention can be represented conventionallyby the following structure: ##STR3## where: h is halogen,

B is an air-dryable group,

Ct is a cationic group,

n is at least 2,

m is at least 1, and

p is at least 1.

In the foregoing structure, h preferably is chlorine or bromine, B is anair-dryable group as described above, and Ct is a cationic group whichpreferably is a cationized amine or thiol. Also, n preferably is 4, andm and p are 1.

A preferred cationic surfactant of the present invention can berepresented by the following structure: ##STR4## where: Ct¹ is acationic-containing group and B¹ is an air-dryable group.

Synthesis schemes for forming the cationic surfactants as shown aboveinclude the reaction of an amine with a monofunctional epoxy ormultifunctional epoxy wherein desirably the epoxy contains apolyhalogenated group for providing a degree of flame-retardancy ornon-flame-promoting capability to the ultimate surfactant reactionproduct. Alternatively, an amine or thiol can be reacted with analpha-,beta-ethylenically unsaturated carbonyl group by a conventionalMichael addition for forming the cationic surfactant. The preferredethylenically unsaturated carbonyl compound will be a bis-maleimide, anacrylate, or an acrylamide as those skilled in this art will appreciate.The thus-formed reaction product then can be neutralized with aproton-donating or protic acid for converting the amine group into acorresponding ammonium group for providing the cationic functionalityrequired of the cationic surfactant. A thiol will be converted into asulfonium group most readily with acid and halogen or with an alkylhalide (e.g. methyl iodide). Typical protic acids for this purposeinclude, for example, acetic acid, lactic acid, hydrochloric acid,formic acid, and like conventional organic and inorganic proton-donatingacids, especially those shown in the cathodic electrocoating art.

It should be noted that relative to the novel cationic surfactants ofthe present invention, work on the present invention revealed a uniquediscovery relative to conventional flame-retardant epoxy resin coatingcompositions cured with a polyamine or polyamide hardener. Such coatingcompositions while curable at room temperature have certain organiccomponents thereof which are emissive during the curing step. Initialanalysis of this problem evolved the hypothesis that the polyamidehardener contained certain low molecular weight, mobile amine componentswhich volatilize during the curing of the film of the composition atroom temperature. Applying the technology generated for production ofthe novel cationic surfactants of the present invention led to effortswherein specific compositionally-similar trapping agents were added tothe polyamide hardener in order to attempt to trap such volatile mobileamine components. Results of such tests unexpectedly revealed that thetrapping agents preferentially reacted with the low molecular weight,emissive amine components of the polyamide hardener to the exclusion ofthe desired high molecular weight polyamine and polyamide components ofthe hardener. Accordingly, suitable trapping agents include mono- andpolyfunctional epoxides, optionally halogenated,alpha-,beta-ethylenically unsaturated carbonyl compounds (e.g.acrylates, acrylamides, and bis-maleimides) and similar activated doublebond-containing compounds, and specific epoxy-adducts wherein air-dryingfunctionality is reacted onto the epoxy trapping agent. The similarityof these trapping agents to those compounds useful in forming the novelcationic surfactants of the present invention should be readilyapparent. The resulting reaction product in the polyamine hardener hasbeen determined not to interfere with the curing reaction of the epoxyresin and polyamide hardener and such reaction product is non-emissiveunder curing conditions of the applied film. Such reaction products canbe termed as an intrinsic or in-situ generated internal plasticizer inthe composition, can be protonated with a proton-donating acid to forman intrinsic non-emissive surfactant in the composition, or can containfunctionality for participating in the curing reaction to link into thefilm network of the coating composition. Under any of these conditions,the resulting reaction product or adduct of the trapping agent isnon-emissive, can provide additional flame-retardancy to the coatingcomposition, and even can favorably contribute to the non-volatilesolids content of the coating composition by linking into the polymernetwork. The selectivity of the reaction of the trapping agent for thelow molecular weight amine components is unexpected, but is amplydemonstrated in examples which follow.

The novel non-emissive, non-flame-promoting anionic surfactants of thepresent invention can be synthesized by reaction schemes similar tothose detailed above for the novel non-ionic and cationic surfactants.Such anionic surfactants can be represented generally by the followingstructure: ##STR5## A is an anionic group which preferably is a carboxylanion. The other substituents are the same as they have been describedabove relative to the solvents, non-ionic surfactants, and cationicsurfactants of the present invention. A preferred anionic surfactant canbe represented as follows: ##STR6## where: B¹ is an air-dryable group.

Typical synthesis schemes for manufacturing such anionic surfactantsinclude, for example, the reaction of TCPA with one mole of an alcoholcontaining air-drying or reactive functionality. Of course, HCNDA may besubstituted for TCPA in such synthesis scheme. It will be appreciatedthat other anionic groups, such as sulfate or phosphate, can be utilizedin forming the novel anionic surfactants of the present invention as cana variety of other reactants and reaction schemes.

Coating compositions formulated according to the present inventioncontain the novel surfactant or novel solvent of the present invention,and can contain both the novel solvent and one of the novel surfactantsof the present invention if desired. Resins for forming the coatingcompositions of the present invention are curable at room temperatureand include air-drying resins such as, for example, alkyd resinsincluding modified (e.g. maleinized) alkyd resins. While such alkydresins desirably are polyhalogenated for providing flame-retardancy,such is not necessary as the solvents of the surfactants of the presentinvention can be formulated to provide, at least to some degree,flame-retardancy to the coating composition. Desirably, though, theresins of the coating composition are conventional flame-retardantresins. Another desirable class of resins for the present invention areflame-retardant epoxy resins cured with an amine or amide hardener. Infact, combinations of alkyd resins and epoxy resins can be usedaccording to the precepts of the present invention. Additionally,aqueous based systems of the coating composition can be combined withpolyvinylidene chloride and similar latices.

Other components permissible in the coating composition include water asthe solvent or water in combination with the novel cosolvent of thepresent invention. Not permitted in the coating composition areconventional volatile solvents, conventional volatile surfactants, andlike conventional emissive volatile components normally found in coatingcompositions. Such emissive conventional solvents and surfactants arereplaced by those non-emissive, non-flame-promoting solvents andsurfactants of the present invention. Of course, pigments and fillersmay be included in the coating composition in conventional fashion assuch inert ingredients typically are not emissive.

Certain flame-retardant epoxy resins and alkyd resins, especially thosehighly brominated, have a tendency to crystallize readily out ofsolution and are difficult to emulsify into stable dispersions. Use ofthe novel solvents and surfactants of the present invention can assistin stably dispersing such resins for forming coating compositions whichprovide the requisite properties desired of coating compositions.Another approach to retarding the crystallization of such highlyhalogenated flame-retardant resins involves a technique for interruptingthe crystallinity affinity of such resins. This interruption techniquecan be accomplished by reacting at least a fraction of the resin with along chain hydrocarbyl compound such as a fatty acid. Desirably, suchfatty acid is an air-drying fatty acid such as linoleic or linolenicacid for imposing additional curing ability into the system.Unexpectedly, it was discovered that by modifying such flame-retardantresins, the remainder of the unmodified resin could be readilyemulsified in water to provide a stable dispersion or coatingcomposition. Additionally, such stabilized resin blend could be used aspart of a two-pack system with an amine hardener without the modifiedresin tending to crystallize upon storage thereof. The examples willfully support this embodiment of the invention also.

The following examples show how the present invention can be practicedbut should not be construed as limiting. In this application, allpercentages and proportions are by weight and all units are in themetric system, unless otherwise expressly indicated.

EXAMPLES EXAMPLE 1

One mole (286 grams) of tetrachlorophthalic anhydride (TCPA) was mixedwith one mole (58 grams) of allyl alcohol in a three-neck flask fittedwith a heating jacket, reflux condenser and a stirrer. The mixture washeated up to 92° C. for two hours whereupon one mole (114 grams) ofallyl glycidyl ether and 0.1% by weight benzyldimethyl amine catalystwere added to the flask. This addition caused an immediate exotherm tooccur causing the temperature of the mixture to increase to 140° C.

The reaction mixture was allowed to cool to room temperature. Theresulting product was a clear (100% solids) liquid containing no freeacid functionality. The product solvent can be represented by thefollowing general structure: ##STR7##

Note that the foregoing reaction scheme can be carried out in excessallyl alcohol as the reaction solvent followed by removal of excessallyl alcohol after the addition of the glycidyl allyl alcohol compound.

EXAMPLE 2

The procedure of Example 1 was repeated using hydroxyethyl methacrylatein place of the allyl alcohol as the ring-opening alcohol followed bythe addition of the allyl glycidyl ether compound and 0.1% by weightbenzoquinone as a polymerization inhibitor. The allyl glycidyl etherreaction was carried out to 90% completion followed by filtration of theunreacted TCPA crystals. The resulting, slightly-viscous liquid solventhad no detectable acid functionality and can be representedconventionally by the following general structure: ##STR8##

EXAMPLE 3

The procedure of Example 1 was repeated using trichloroethanol in placeof ally alcohol as the ring-opening alcohol. The resulting clear liquidcan be represented conventionally by the following structure: ##STR9##

EXAMPLE 4

One mole of pentachlorophenol (PCP) was reacted at 40°-60° C. with anexcess of epichlorohydrin and a sodium hydroxide/water dispersion toform the glycidyl ether of PCP. The ether then was reacted with oneequivalent of linoleic acid at 80° C. to form a liquid, non-emissive,air-drying solvent of the following general structure: ##STR10##

EXAMPLE 5

A control, non-flame-retardant, air-drying solvent was synthesized byreacting one mole of styrene oxide with one mole of linoleic acid in thepresence of 0.1% amine catalyst. The control solvent has the followingstructure: ##STR11##

EXAMPLE 6

The air-drying solvents in Examples 1-5 were tested for their emissivityas follows: The solvents were blended with a 100% solids flame-retardantchlorinated alkyd resin [a chlorinated soya oil alkyd marketed asBECKOSOL 13-029 resin from Reichhold Chemical Company] at a 1:1 weightratio. The blends were catalyzed with 0.02% cobalt, 0.015% zirconium,and 0.02% manganese octoate. The catalyzed blends were drawn down ontoglass plates with a number 20 wire-wound rod and allowed to air-dry atroom temperature for 5 days. The glass plates were weighed immediatelyafter application of the coatings and after the 5-day drying periodafter which the applied films were tack-free, hard surface-cured films.Each of the solvents of Examples 1-5 had cured into the applied film ofthe air-drying alkyd as indicated by the weight loss measurements whichshowed that the films had lost between 0 and 2% of their weight afterthe 5-day room temperature curing period. Thus, all 5 coatingsformulations were deemed to be non-emissive.

EXAMPLE 7

The coating compositions formulated in Example 6 next were tested fortheir flame-retardancy. The flame test utilized to determineflame-retardancy involved 1/4" to 1/2" square dry film samples (removedfrom the glass upon which they were cured) which were placed within thegas flame of a Bunsen burner for approximately 1 second. Those filmsamples that immediately extinguished themselves upon removal from theopen flame were designated as flame-retardant. Moreover, goodflame-retardant systems were those which could withstand insertion andremoval from the open flame several times without supporting orpropogating combustion.

The comparative formulations of the air-drying alkyd with driers neatand the 1:1 weight blend of the alkyd and comparative solvent of Example5 both burned rapidly in the flame and continued burning outside theflame. Thus, these formulations support combustion and are notflame-retardant. The novel compositions of alkyd and solvents ofExamples 1-4 burned in the flame but immediately extinguished themselvesupon removal from the flame, even upon repeated insertion and removalfrom the open flame. Thus, the novel compositions containing the novelsolvents of Examples 1-4 definitely are flame-retardant.

EXAMPLE 8

One mole of TCPA was reacted with one mole of the reaction product ofone mole of linoleic acid and one mole of propylene oxide to form anon-emissive, non-flame-promoting anionic surfactant having thefollowing structure: ##STR12## The reaction was conducted intetrahydrofurnan (THF) solvent which was removed from the reactionproduct after its formation. Progress of the reaction was monitored byKOH titration techniques until one-half of the equivalent weight of theTCPA was determined to have been consumed.

EXAMPLE 9

A practical paint using the anionic surfactant of Example 8 can be madefrom the following ingredients.

                  TABLE I                                                         ______________________________________                                                       Paint A      Paint B                                           Ingredient     (Parts by weight)                                                                          (Parts by weight)                                 ______________________________________                                        Beckosol 13-029 resin                                                                        66.70        82.00                                             Demineralized Water                                                                          140.00       25.00                                             Cobalt Catalox 0.10         0.13                                              Zirconium Catalox                                                                            0.07         0.09                                              Manganese Octoate                                                                            0.20         0.26                                              Polywet AX-4 surfactant                                                                      7.50         4.80                                              Anionic Surfactant of                                                                        3.00         2.00                                              Ex. 8                                                                                        217.57       114.28                                            ______________________________________                                         Beckosol 13029, a chlorinated alkyd of Reichhold Chemical Co., was            stripped to 90% solids.                                                       Cobalt Catalox, 12% active metal drier supplied by Ferro Chemical.            Zirconium Catalox, 12% active metal drier supplied by Ferro Chemical          Manganese Octoate, 6% active metal drier supplied by Shepard Chemical         Polywet AX4, 40% active anionic surfactant supplied by Uniroyal          

In formulating both paints, the Beckosol alkyd resin was heated in awater bath to about 70° C. and positioned on a Premier mill. The waterand anionic surfactant (neutralized to pH of 8 with NH₄ OH), also heatedto 160° F., then were slowly added to the heated alkyd resin under highshear agitation to form a stable emulsion. In Paint A, the Polywetwetting agent was added to the water before the resin emulsificationstep, while in Paint B, the wetting agent was added after the resinemulsification step.

Both paints demonstrated excellent stability and good dispersioncharacteristics. Both paints also demonstrated good applicationcharacteristics onto wood plaques and dried into continuous films havingexcellent hardness and flame retardant capability.

EXAMPLE 10

A non-emissive, non-flame-promoting nonionic surfactant was prepared byreacting the anionic surfactant of Example 8 (1 mole) with 4 moles ofpropylene oxide in the presence of BF₃ -etherate cationic catalyst. Thenonionic surfactant had the following structure: ##STR13##

EXAMPLE 11

A curable, non-emissive, non-flame-promoting cationic surfactant wasprepared by reacting 1 mole of DER 552 epoxy resin (Dow Epoxy Resin,40%-50% bromine content, epoxide equivalent weight of 305-355, DowChemical Company, Midland, Mich.) with 1 mole of morpholine. Thesurfactant reaction product can be represented as follows: ##STR14## Thesurfactant can be neutralized with acid, e.g. acetic acid, to form thecationized form of the surfactant.

EXAMPLE 12

In order to evaluate the selective reaction of the various trappingagents with the low molecular weight mobile amine components ofconventional polyamide hardeners, several trapping agents were reactedwith VERSAMID 125 polyamide hardener (a liquid polyamide having anequivalent weight of 190 supplied by General Mills, Minneapolis, Minn.The modified, non-emissive hardeners were formulated into coatingcompositions with flame-retardant epoxy resins, and applied films of thecoating compositions tested in order to determine whether themodification to the hardener would interfere with the performance of thecuring reaction. The following table displays the results obtained.

                                      TABLE 2                                     __________________________________________________________________________           EPOXY RESIN                                                                              HARDENER TRAPPING AGENT                                     RUN NO.                                                                              Type  Wt (gms)                                                                           Type                                                                              Wt (gms)                                                                           Type    Wt (gms)                                                                           RESULTS                               __________________________________________________________________________    CONTROL                                                                              EPON 828                                                                            5    V-125                                                                             5    --      --   Full Cure in 3 days                   1      EPON 828                                                                            5    V-125                                                                             5    Epichlorhydrin                                                                        0.5  Full Cure in 3 days                   2      EPON 828                                                                            5    V-125                                                                             5    Epichlorhydrin                                                                        0.5  Full Cure in 3 days                   3      EPON 828                                                                            5    V-125                                                                             5    Araldite 8047                                                                         0.5  Full Cure in 3 days                   4      EPON 828                                                                            5    V-125                                                                             5    Araldite 8047                                                                         1.0  Full Cure in 3 days                   5      EPON 828                                                                            5    V-125                                                                             5    Araldite 8047                                                                         1.0  Full Cure in 3 days                                              Diethyl Amine                                                                         1.0                                        __________________________________________________________________________     EPON 828 is a diglycidyl ether of bisphenol A, epoxide equivalent weight      of 185-192, Shell Chemical Company.                                           V125 is Versemid 125 liquid polyamide.                                        Araldite 8047 is a brominated epoxy resin, epoxy equivalent weight of         223-246, about 20% bromine content, CibaGeigy.                           

EXAMPLE 13

The modified Versamid 125 hardener of Example 12 was characterizedfurther as to the selectivity of the trapping agents for preferentiallyreacting with the volatile amine components thereof. Initially, theVersamid 125 hardener was subjected to liquid chromatography (LC) inorder to generate an LC chromatogram thereof. The LC chromatogramrevealed a major peak and a minor peak having a relative peak heighthratio of 18:2. The minor peak is believed to be the emissive, lowmolecular weight components of the hardener. Monitoring of the minorpeak and its ratio to the major peak upon reaction with the trappingagents should reveal the selectivity of the reaction.

The various modified hardeners of Example 12 were subjected to liquidchromatography and the LC chromatogram evaluated. For each of thetrapping agnets used, the relative peak heighths of the major peaks tothe minor peaks increased to 14,400:4. Clearly, the selectivity of thetrapping agent reaction is demonstrated.

We claim:
 1. A cationic, non-emissive, non-flame promoting, room-temperature curable surface-active agent which comprises a polyhalogenated compound containing a cationic group and a room-temperature curable group selected from the group consisting of an oxirane group, an air-dryable group derived from an air-dryable fatty acid, an air-dryable allyl ether group, and combinations thereof.
 2. The cationic agent of claim 1 which is represented by the following structure: ##STR15## where: h is a halogen,B is said room-temperature curable group, Ct is a cationic group, n is at least 2, m is at least 1, and p is at least
 1. 3. The cationic agent of claim 1 which is the cationized reaction product of a cationizable compound and a polyhalogenated, room-temperature curable compound.
 4. The cationic agent of claim 2 wherein B is an oxirane-functional group, an allyl ether group, or an air-dryable group derived from a fatty acid; h is chlorine or bromine; and Ct is an ammonium or sulfonium group.
 5. The cationic agent of claim 2 represented by the following structure: ##STR16## where: Ct¹ is a cationic-containing group and B¹ is said room-temperature curable organic group.
 6. The cationic agent of claim 5 wherein h is chlorine.
 7. The cationic agent of claim 3 wherein said cationizable compound is a cationizable nitrogen-containing compound and said polyhalogenated compound is a polyhalogenated polyepoxide or a polyhalogenated alpha-, beta-ethylenically unsaturated carbonyl compound. 